CN111040688A - Lignin-based phenolic resin adhesive synergistically modified by polyphenol compound and phenol - Google Patents
Lignin-based phenolic resin adhesive synergistically modified by polyphenol compound and phenol Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
Abstract
The invention discloses a lignin-based phenolic resin adhesive synergistically modified by polyphenol compounds and phenol. The invention adopts a polyphenol compound, phenol and lignin to react to prepare lignin synergistically modified by the polyphenol compound and the phenol, and prepares the polyphenol compound and the lignin synergistically modified by the phenol based phenolic resin adhesive by reacting the modified lignin and formaldehyde. According to the invention, the lignin is synergistically modified by the polyphenol compound and the phenol, the lignin activity is activated, the curing crosslinking point is increased, and the modified lignin-based phenolic resin adhesive obtained by the reaction of the modified lignin and the formaldehyde keeps the advantages of better heat resistance, corrosion resistance and the like, and can also reduce the curing temperature and energy consumption; in addition, the content of free phenol and free formaldehyde in the modified lignin-based phenolic resin adhesive is greatly reduced, and the bonding strength is also improved.
Description
Technical Field
The invention relates to a lignin-based phenolic resin adhesive synergistically modified by polyphenol compounds and phenol, belonging to the technical field of material chemistry.
Background
The phenolic resin is prepared by condensation polymerization of phenols and aldehydes, and a plywood product prepared by the phenolic resin adhesive has the advantages of high bonding strength, weather resistance, water resistance, corrosion resistance and the like. However, the price of phenol as a raw material rises along with the shortage of petroleum resources, which directly results in higher price of the phenolic resin adhesive. Meanwhile, because the preparation process of the phenolic resin adhesive is unreasonable, a certain amount of formaldehyde can be released in the production and use processes, and the formaldehyde can cause various diseases of a human body, such as asthma, tracheitis, dermatitis and the like, and even can cause malignant tumors after long-term contact. In addition, phenol, which is one of the raw materials, is also highly toxic. Due to the existence of the factors, the use of the phenolic resin adhesive in China is limited to a certain extent.
Lignin itself is a phenolic polymer that is present in plants together with cellulose and hemicellulose, and acts as a binder in plants. The lignin molecules have a large number of phenolic structural units with active sites, and can participate in the reaction in the glue-making reaction, so that the lignin molecules can replace phenol to be applied to the preparation of phenolic resin adhesives to a certain extent. The lignin is renewable, nontoxic, degradable, wide in source and low in cost, so that the lignin is regarded as an excellent green and environment-friendly chemical raw material. As an organic renewable resource, the lignin has functional groups such as hydroxyl, carboxyl and the like, and can be subjected to reactions such as alkylation, esterification, acylation and the like, so that the lignin can replace phenols to react with aldehydes to react with phenol, and the lignin can replace a part of phenol to react with formaldehyde. Because lignin has multiple sources and is cheap, partial substitution of petrochemicals (phenols) by lignin can reduce production cost to a great extent, but the reaction activity of lignin is inferior to that of phenol, which affects the normal reaction of phenol and formaldehyde. However, the phenolic lignin phenolic resin adhesive needs higher curing temperature and slower curing speed in use, thereby greatly limiting the application field of the phenolic lignin phenolic resin adhesive.
Disclosure of Invention
In order to solve the technical problems, the invention provides a lignin-based phenolic resin adhesive modified by a polyphenol compound and phenol cooperatively. According to the invention, the lignin is synergistically modified by the polyphenol compound and the phenol, the lignin activity is activated, the curing crosslinking point is increased, and the modified lignin-based phenolic resin adhesive obtained by the reaction of the modified lignin and the formaldehyde keeps the advantages of better heat resistance, corrosion resistance and the like, and can also reduce the curing temperature and energy consumption; in addition, the content of free phenol and free formaldehyde in the modified lignin-based phenolic resin adhesive is greatly reduced, and the bonding strength is also improved.
The first purpose of the invention is to provide a preparation method of a lignin-based phenolic resin adhesive synergistically modified by a polyphenol compound and phenol, which comprises the following steps: reacting a polyphenol compound, phenol and lignin to prepare lignin synergistically modified by the polyphenol compound and the phenol, and reacting the modified lignin with formaldehyde to prepare the resorcinol and phenol synergistically modified lignin-based phenolic resin adhesive.
Further, the mass ratio of the phenol to the lignin is 9.5:0.5-2:8, and the mass ratio of the polyphenol compound to the phenol is 0.05:1-1: 1.
Further, putting the raw materials of the polyphenol compound, the phenol and the lignin into a reaction kettle according to the proportion, adding water with the mass of 3-5 times of that of the raw materials, adjusting the pH value to 11-14, and reacting for 1-2 hours at 50-70 ℃.
Further, the pH was adjusted by adding sodium hydroxide.
Further, the polyphenol compound is 5,5',6,6',7,7',8,8' -octahydro-1, 1 '-di-2-naphthol, xylenol blue, dienestrol, honokiol, resorcinol, bisphenol A, phenol red, phenolphthalein, catechol violet, tert-butylhydroquinone, xylenol blue, 1, 2-benzenediol, 1, 4-benzenediol, 2, 6-naphthalenediol, 1, 3-naphthalenediol, 1, 4-naphthalenediol, 2' -biphenol, 2, 7-dihydroxynaphthalene, 2-methylresorcinol, 3-methylcatechol, 4-ethylphosphonobhenol, 4-ethylresorcinol, quinine, anthracrinol, methylhydroquinone, 1, 8-naphthalenediol, 4-n-hexylresorcinol, alizarin, indoxyl, cinnarizine, cinnamyl phenol, 2-methoxy hydroquinone, 5-methoxy resorcinol, 2-n-propyl resorcinol, 4-tert-octyl resorcinol, 2, 6-dihydroxybenzoic acid, phloretin, 5-methyl pyrogallol, phloroglucinol, 1,2, 3-trisphenol, 1,2, 4-benzenetrisphenol, 1,8, 9-trihydroxy anthracene, 4' -methylene trisphenol, 2,4, 6-trihydroxy acetophenone, anthocyanin compounds, flavanol compounds, flavonoid compounds, trace flavonoid compounds, isoflavonoid compounds and brass tannin compounds.
Furthermore, the molar ratio of the formaldehyde to the phenolic hydroxyl in the modified lignin is 1: 1-2.5: 1.
Further, the specific steps of the reaction of the synergistically modified lignin and formaldehyde comprise: adding 60-90% of total formaldehyde into the modified lignin, carrying out pre-reaction for 0.5-1.5 h at 85-90 ℃, then adding the residual formaldehyde, and carrying out reaction for 2-4 h at 55-75 ℃.
The second purpose of the invention is to provide the polyphenol compound and phenol prepared by the method for synergistically modifying the lignin-based phenolic resin adhesive.
The invention has the beneficial effects that:
according to the invention, the lignin is synergistically modified by the polyphenol compound and the phenol, and compared with the phenol, the polyphenol compound is rich in phenolic hydroxyl groups, so that the modified lignin has more active phenolic hydroxyl groups; compared with the polyphenol compound, the phenol has the advantage of small molecular size and is easy to modify the place with larger steric hindrance of lignin. The two components have synergistic effect, so that the phenolization efficiency is higher, the lignin activity is activated, the curing crosslinking point is increased, and the modified lignin-based phenolic resin adhesive obtained by the reaction of the modified lignin and formaldehyde keeps the advantages of better heat resistance, corrosion resistance and the like, and can also reduce the curing temperature and energy consumption; in addition, the content of free phenol and free formaldehyde in the modified lignin-based phenolic resin adhesive is greatly reduced, and the bonding strength is also improved.
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FIG. 1 is an infrared spectrum of lignin before and after modification.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
And (3) determining the content of phenolic hydroxyl groups of lignin: FC method
And (3) measuring the viscosity of the adhesive: reference national standard GB/T14074-2017
And (3) solid content determination of the adhesive: reference national standard GB/T14074-2017
And (3) determining the content of free formaldehyde of the adhesive: reference national standard GB/T14074-2017
And (3) determining the content of free phenol of the adhesive: liquid chromatography, weighing 0.5g (accurate to 0.0001) of phenol in a beaker, adding water, stirring to dissolve, transferring to a 500mL volumetric flask, washing the beaker with water for 2-3 times, transferring all washing liquid into the volumetric flask, diluting with water to a scale mark, respectively sucking 1.0, 2.0, 3.0, 4.0, 5.0 and 6.0mL, placing in a 100mL volumetric flask, adding water to the scale mark, and shaking uniformly. And (3) respectively taking the solution 20 mu 1, injecting into a liquid chromatograph, recording a phenol chromatographic peak and calculating a peak area, performing linear regression on the sample injection amount (X) by using the peak area (Y) to obtain a regression equation, taking about 0.5g of a phenolic resin sample, diluting to a 500mL volumetric flask, taking the solution 20 mu 1, injecting into the liquid chromatograph, recording the chromatographic peak and calculating the peak area, and contrasting a correction curve to obtain the content of free phenol.
Adhesive bonding strength determination: refer to the technical specification of the glued wood structure of GBT 50708-.
Infrared absorption spectrum determination: after drying the sample at 80 ℃, the sample was mixed with potassium bromide (the weight ratio of sample to potassium bromide was about 1:100), ground under the irradiation of an infrared lamp for 20min, pressed into a sheet at about 5Mpa, and subjected to infrared testing.
Example 1: synergistic modification of 1, 2-benzenediol and phenol of lignin
Mixing lignin, phenol and 1, 2-benzenediol (m)Lignin:mPhenol and its preparation:m1, 2-benzenediolPut 4:6:1.5) into a 250ml three-necked flask, add water (m)Water (W):mFixing device4:1) in a flask, add sodium hydroxide to adjust the pH to 13. Heating and refluxing for reaction for 1.5h at the constant temperature of 60 ℃ under the stirring action. And after the reaction is stopped, cooling to room temperature to obtain the lignin stock solution synergistically modified by the 1, 2-benzenediol and the phenol.
The modified and unmodified lignin was subjected to IR absorption spectroscopy, and the results are shown in FIG. 1, which shows that lignin has similar IR spectra before and after modification, wherein 2919cm-1Absorption peaks corresponding to methyl, methylene (C-H); 1536cm-1、1512cm-1Corresponding to the vibration peak of a C-skeleton of a benzene ring; 1232cm-1Corresponding to the vibration peak of the phenolic hydroxyl (O-H), the absorption peak of the phenolized lignin at the peak is enhanced, which shows that the phenolic hydroxyl content of the modified lignin is increased, 1135cm-1The absorption peak of the modified lignin at this point was reduced in response to stretching vibration of methoxy groups (C-O), indicating that the methoxy group content of the lignin was reduced after modification. FIG. 1 shows that phenolated lignin has more active sites and fewer inert groups and is more suitable for preparing phenolic resin adhesives than unmodified lignin.
The lignin phenolic hydroxyl group content before and after modification was measured, and the results are shown in table 1.
TABLE 1 Lignin phenolic hydroxyl content before and after modification
The modification is carried out so that the phenolic hydroxyl group of lignin is 1.775mmol-1The concentration was increased to 4.129mmol.g-1The reaction activity of the modified lignin is increased by 132 percent, and the modified lignin is more suitable for preparing the phenolic resin adhesive.
Example 2: preparation of lignin-based phenolic resin adhesive cooperatively modified by 1, 2-benzenediol and phenol
The modified lignin stock solution prepared in example 1 was added dropwise to formaldehyde in a molar ratio of formaldehyde to phenolic hydroxyl of 2:1 by using a constant pressure dropping funnel, 80% of the total amount of formaldehyde was added first, and the mixture was reacted at 90 ℃ for 1 hour. And then adding the rest 20 percent of formaldehyde, and reacting for 3 hours at 65 ℃ to obtain the lignin-based phenolic resin adhesive synergistically modified by the 1, 2-benzenediol and the phenol.
Example 3: preparation of lignin-based phenolic resin adhesive cooperatively modified by 1, 2-benzenediol and phenol
Mixing lignin, phenol and 1, 2-benzenediol (m)Lignin:mPhenol and its preparation:m1, 2-benzenediolPut 4:6:1.5) into a 250ml three-necked flask, add water (m)Water (W):mFixing device4:1) in a flask, add sodium hydroxide to adjust the pH to 13. Heating and refluxing for reaction for 1.5h at the constant temperature of 60 ℃ under the stirring action. And after the reaction is stopped, cooling to room temperature to obtain the lignin stock solution synergistically modified by the 1, 2-benzenediol and the phenol.
The modified lignin stock solution prepared by the method is added with formaldehyde by a constant pressure dropping funnel according to the molar ratio of the formaldehyde to the phenolic hydroxyl of 2:1, 80 percent of the total amount of the formaldehyde is added firstly, and the reaction is carried out for 1 hour at 85 ℃. And then adding the rest 20 percent of formaldehyde, and reacting for 3 hours at 70 ℃ to obtain the lignin-based phenolic resin adhesive synergistically modified by the 1, 2-benzenediol and the phenol.
According to the invention, the pre-reaction is carried out at a pre-reaction temperature of 85-90 ℃, and at a higher pre-reaction temperature, the polycondensation reaction speed is increased compared with the lengthening reaction speed, the macromolecule formation speed is increased, the molecular weight is increased, and the bonding strength is also increased; and then reacting at 60-70 ℃, and reacting at a proper temperature, so that on one hand, phenolic hydroxyl and formaldehyde are reacted quickly, the content of free phenol and free formaldehyde is reduced, and on the other hand, the problems that the temperature is too high, the fluidity of resin is poor, and the bonding strength is reduced are avoided.
Example 4: preparation of resorcinol and phenol synergistically modified lignin-based phenolic resin adhesive
Mixing lignin, phenol and resorcinol (m)Lignin:mPhenol and its preparation:mResorcinolPut 4:6:1.5) into a 250ml three-necked flask, add water (m)Water (W):mFixing device4:1) in a flask, add sodium hydroxide to adjust the pH to 13. Heating at 60 deg.C under stirringThe flow reaction was 1.5 h. And after the reaction is stopped, cooling to room temperature to obtain the resorcinol and phenol synergistic modified lignin stock solution.
The modified lignin stock solution prepared by the method is added with formaldehyde by a constant pressure dropping funnel according to the molar ratio of the formaldehyde to the phenolic hydroxyl of 2:1, 80 percent of the total amount of the formaldehyde is added firstly, and the reaction is carried out for 1 hour at 90 ℃. And then adding the residual 20 percent of formaldehyde, and reacting for 3 hours at 65 ℃ to obtain the resorcinol and phenol synergistically modified lignin-based phenolic resin adhesive.
Example 5: preparation of bisphenol A and phenol synergistic modified lignin-based phenolic resin adhesive
Mixing lignin, phenol and bisphenol A (m)Lignin:mPhenol and its preparation:mBisphenol APut into a 250ml three-neck flask with 4:6:2), add water (m)Water (W):mFixing device4:1) in a flask, add sodium hydroxide to adjust pH to 12. Heating and refluxing for reaction for 1h at the constant temperature of 70 ℃ under the stirring action. And after the reaction is stopped, cooling to room temperature to obtain the bisphenol A and phenol synergistic modified lignin stock solution.
The modified lignin stock solution prepared by the method is added with formaldehyde by a constant pressure dropping funnel according to the molar ratio of the formaldehyde to the phenolic hydroxyl of 2.5:1, 80 percent of the total amount of the formaldehyde is added firstly, and the reaction is carried out for 1 hour at 85 ℃. And then adding the rest 20 percent of formaldehyde, and reacting for 3 hours at 65 ℃ to obtain the bisphenol A and phenol synergistically modified lignin-based phenolic resin adhesive.
Example 6: preparation of lignin-based phenolic resin adhesive cooperatively modified by 2-methylresorcinol and phenol
Mixing lignin, phenol and 2-methylresorcinol (m)Lignin:mPhenol and its preparation:m2-MethylresorcinolPut into a 250ml three-neck flask with 4:6:1, add water (m)Water (W):mFixing device4:1) in a flask, add sodium hydroxide to adjust the pH to 14. Heating and refluxing for reaction for 2h at the constant temperature of 50 ℃ under the stirring action. And after the reaction is stopped, cooling to room temperature to obtain the 2-methylresorcinol and phenol synergistic modified lignin stock solution.
The modified lignin stock solution prepared by the method is dripped into formaldehyde by a constant pressure dropping funnel according to the molar ratio of the formaldehyde to the phenolic hydroxyl of 2:1, 70 percent of the total amount of the formaldehyde is firstly added, and the reaction is carried out for 0.5h at the temperature of 90 ℃. And then adding the rest 30 percent of formaldehyde, and reacting for 4 hours at 70 ℃ to obtain the 2-methylresorcinol and phenol synergistically modified lignin-based phenolic resin adhesive.
Comparative example 1:
mixing lignin and phenol (m)Lignin:mPhenol and its preparationPut 4:6) into a 250ml three-necked flask, add water (m)Water (W):mFixing device4:1) in a flask, add sodium hydroxide to adjust the pH to 13. Heating and refluxing for reaction for 1.5h at the constant temperature of 60 ℃ under the stirring action. And after the reaction is stopped, cooling to room temperature to obtain the phenol modified lignin stock solution.
The modified lignin stock solution prepared by the method is added with formaldehyde by a constant pressure dropping funnel according to the molar ratio of the formaldehyde to the phenolic hydroxyl of 2:1, 80 percent of the total amount of the formaldehyde is added firstly, and the reaction is carried out for 1 hour at 90 ℃. And then adding the rest 20 percent of formaldehyde, and reacting for 3 hours at 65 ℃ to obtain the phenol modified lignin-based phenolic resin adhesive.
Comparative example 2:
mixing lignin and 1, 2-benzenediol (m)Lignin:m1, 2-benzenediolPut 4:1.5) into a 250ml three-necked flask, water (m) was addedWater (W):mFixing device4:1) in a flask, add sodium hydroxide to adjust the pH to 13. Heating and refluxing for reaction for 1.5h at the constant temperature of 60 ℃ under the stirring action. And after the reaction is stopped, cooling to room temperature to obtain the 1, 2-benzenediol modified lignin stock solution.
The modified lignin stock solution prepared by the method is added with formaldehyde by a constant pressure dropping funnel according to the molar ratio of the formaldehyde to the phenolic hydroxyl of 2:1, 80 percent of the total amount of the formaldehyde is added firstly, and the reaction is carried out for 1 hour at 90 ℃. And then adding the rest 20 percent of formaldehyde, and reacting for 3 hours at 65 ℃ to obtain the 1, 2-benzenediol modified lignin-based phenolic resin adhesive.
The lignin-based phenolic resin adhesives prepared in examples 2-6 and comparative examples 1-2 were subjected to performance tests, and the results are shown in table 2:
TABLE 2 Properties of Lignin-based phenolic resin Adhesives
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (8)
1. A preparation method of a lignin-based phenolic resin adhesive synergistically modified by a polyphenol compound and phenol is characterized by comprising the following steps: reacting a polyphenol compound, phenol and lignin to prepare lignin synergistically modified by the polyphenol compound and the phenol, and reacting the modified lignin with formaldehyde to prepare the polyphenol compound and phenol synergistically modified lignin-based phenolic resin adhesive.
2. The method according to claim 1, wherein the mass ratio of the phenol to the lignin is 9.5:0.5-2:8, and the mass ratio of the polyphenol compound to the phenol is 0.05:1-1: 1.
3. The method according to claim 2, characterized in that the raw materials of the polyphenol compound, the phenol and the lignin are placed in a reaction kettle according to the proportion, water with the mass of 3-5 times that of the raw materials is added, the pH is adjusted to 11-14, and the reaction is carried out for 1-2 hours at 50-70 ℃.
4. The method of claim 3, wherein the pH is adjusted by the addition of sodium hydroxide.
5. The method of claim 1, wherein the polyphenolic compound is 5,5',6,6',7,7',8,8' -octahydro-1, 1 '-di-2-naphthol, xylenol blue, dienestrol, honokiol, resorcinol, bisphenol A, phenol red, phenolphthalein, catechol violet, tert-butylhydroquinone, xylenol blue, 1, 2-benzenediol, 1, 4-benzenediol, 2, 6-naphthalenediol, 1, 3-naphthalenediol, 1, 4-naphthalenediol, 2' -biphenol, 2, 7-dihydroxynaphthalene, 2-methylresorcinol, 3-methylcatechol, 4-ethylphosphodiphenol, 4-ethylresorcinol, quinizarine, anthracrinol, methylhydroquinone, 1, 8-naphthalenediol, 2, 7-dihydroxynaphthalene, 2-methylresorcinol, 3-methylphthalenediol, 4-ethylphosphonobydroquinone, 4-ethylresorcinol, quinizarine, anthraquinoxaline, methylhydroquinone, hydroquinone, 4-n-hexylresorcinol, 2-methoxyhydroquinone, 5-methoxyresorcinol, 2-n-propylresorcinol, 4-tert-octylresorcinol, 2, 6-dihydroxybenzoic acid, phloretin, 5-methylphthalic tris-phenol, phloroglucinol, 1,2, 3-trisphenol, 1,2, 4-benzenetrisphenol, 1,8, 9-trihydroxyanthracene, 4' -methylenetrisphenol, 2,4, 6-trihydroxyacetophenone, anthocyanin compounds, flavanol compounds, flavonoid compounds, trace flavonoid compounds, isoflavonoid compounds and brass tannin compounds.
6. The method according to claim 1, wherein the molar ratio of the formaldehyde to the phenolic hydroxyl groups in the modified lignin is 1:1 to 2.5: 1.
7. The method according to claim 6, wherein the step of reacting the synergistically modified lignin with formaldehyde comprises: adding 60-90% of total formaldehyde into the modified lignin, carrying out pre-reaction for 0.5-1.5 h at 85-90 ℃, then adding the residual formaldehyde, and carrying out reaction for 2-4 h at 55-75 ℃.
8. The polyphenol compound and phenol synergistically modified lignin-based phenolic resin adhesive prepared by the method of any one of claims 1 to 7.
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